WO2016127572A1 - High figure of merit p-type fenbhfsb thermoelectric material and preparation method therefor - Google Patents

High figure of merit p-type fenbhfsb thermoelectric material and preparation method therefor Download PDF

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WO2016127572A1
WO2016127572A1 PCT/CN2015/084262 CN2015084262W WO2016127572A1 WO 2016127572 A1 WO2016127572 A1 WO 2016127572A1 CN 2015084262 W CN2015084262 W CN 2015084262W WO 2016127572 A1 WO2016127572 A1 WO 2016127572A1
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thermoelectric material
value
type
sintering
ingot
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朱铁军
付晨光
赵新兵
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浙江大学
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Priority to US15/539,316 priority patent/US10553771B2/en
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
    • H10N10/80—Constructional details
    • H10N10/85—Thermoelectric active materials
    • H10N10/851—Thermoelectric active materials comprising inorganic compositions
    • H10N10/853—Thermoelectric active materials comprising inorganic compositions comprising arsenic, antimony or bismuth
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C30/00—Alloys containing less than 50% by weight of each constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C33/00—Making ferrous alloys
    • C22C33/02—Making ferrous alloys by powder metallurgy
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C33/00—Making ferrous alloys
    • C22C33/02—Making ferrous alloys by powder metallurgy
    • C22C33/0257—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements
    • C22C33/0278—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements with at least one alloying element having a minimum content above 5%
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
    • B22F2998/10—Processes characterised by the sequence of their steps
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy

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  • the invention relates to the field of semiconductor thermoelectric materials, in particular to a high-quality P-type FeNbHfSb thermoelectric material and a preparation method thereof.
  • thermoelectric material is a semiconductor material that directly converts electrical energy and thermal energy into each other through movement of carriers (electrons or holes) inside the material.
  • the thermoelectric material can convert the thermal energy into the electric energy output, which is called the Seebeck effect; and after the electric field is applied to both ends of the thermoelectric material, the thermoelectric material can convert the electric energy into heat energy, and one end radiates heat.
  • the other end of the heat absorption, known as the Petier effect these two effects make thermoelectric materials have a wide range of applications in power generation or refrigeration.
  • thermoelectric materials can be used as power sources for deep spacecraft, field operations, marine lighthouses, nomadic people, or for industrial waste heat and waste heat power generation.
  • the refrigerating device made of thermoelectric material is small in size and does not require chemical medium, and can be applied to local cooling of small refrigerators, computer chips and laser detectors, medical portable ultra-low temperature refrigerators, etc., and a wider range of potential application fields will include: household Refrigerator, cooling, car or home air conditioning units.
  • the device made of thermoelectric material has the advantages of no mechanical moving parts, no noise, no wear, simple structure, and the shape can be designed as needed.
  • thermoelectric merit The performance of thermoelectric materials is characterized by the "thermoelectric merit" – zT:
  • ⁇ is the thermoelectric potential coefficient of the material
  • ⁇ is the electrical conductivity
  • T is the absolute temperature
  • ⁇ is the thermal conductivity
  • thermoelectric material should have high electrical conductivity and thermoelectric potential coefficient and low thermal conductivity.
  • High-performance thermoelectric devices require N-type and P-type materials with matching performance and structure.
  • thermoelectric materials have important applications in the automotive industry, waste heat recovery in factories, and space satellites.
  • a typical high-temperature power generation thermoelectric material is a SiGe alloy, and its N-type material has high performance, and the zT value is about 1.0, but the P-type material has poor performance, about 0.5.
  • the Half-Heusler system has attracted the attention of researchers in the field of thermoelectrics due to its rich content of components and good electrical properties.
  • the N-type ZrNiSn-based Half-Heusler material has a zT value of 1.0, which is comparable to N-type SiGe.
  • the performance of P-type Half-Heusler materials is still low, which is a major problem that restricts the application of this system in high-temperature power generation.
  • thermoelectric materials The raw materials of FeNbHfSb thermoelectric materials are abundant in the earth's crust and the price is relatively low. However, at present, there are few studies on such thermoelectric materials.
  • the invention provides a novel high-quality P-type FeNbHfSb thermoelectric material and a preparation method thereof, and the highest zT value of the P-type FeNbHfSb thermoelectric material is about 1.45 at 1200K.
  • the invention also discloses a preparation method of the P-type FeNbHfSb thermoelectric material, the steps are as follows:
  • the ingot obtained in the step (1) is pulverized into pellets, and then sintered to obtain the P-type FeNbHfSb thermoelectric material.
  • the raw material is smelted by suspension smelting for 2 to 5 times to obtain an ingot. More preferably, it is 3 times.
  • the ingot is pulverized into particles having a particle diameter of 200 nm to 10.0 ⁇ m; more preferably 200 nm to 2.0 ⁇ m. Particles of this size help the subsequent sintered samples to have lower thermal conductivity, resulting in higher thermoelectric properties.
  • the sintering conditions are preferably 800-900 ° C, 60-70 MPa, and the sintering time is 10-15 min; and further preferably, sintering at 850 ° C and 65 MPa for 10 min, The P-type FeNbHfSb thermoelectric material. If the sintering temperature is too low or the pressure is too small, the density of the sample will be too low, which will lead to a decrease in the conductivity of the material, which is unfavorable. For high performance samples. The sintering time should not be too long, otherwise the grain size of the sintered sample may continue to grow, resulting in an increase in thermal conductivity and a decrease in performance.
  • the present invention has the following beneficial effects:
  • the invention prepares a high-quality P-type FeNbHfSb thermoelectric material, and its maximum zT value reaches 1.45 at 1200K, which is the highest performance obtained in the current P-type Half-Heusler system.
  • the P-type FeNbHfSb thermoelectric material prepared by the invention has abundant reserves of elements contained in the material composition, and therefore, the production cost is relatively low.
  • the P-type FeNbHfSb thermoelectric material has high temperature stability, simple preparation process, short production cycle and high production efficiency.
  • Example 1 is an XRD pattern of FeNb 0.86 Hf 0.14 Sb prepared in Example 1 and FeNb 0.88 Hf 0.12 Sb prepared in Example 2.
  • Example 2a is a graph showing the change of thermal conductivity ⁇ with temperature of the FeNb 1-x Hf x Sb sample prepared in Example 1-7.
  • 2b is a graph showing the change in electrical conductivity ⁇ of the FeNb 1-x Hf x Sb sample prepared in Example 1-7 as a function of temperature.
  • 2c is a graph showing the Seebeck coefficient ⁇ as a function of temperature for the FeNb 1-x Hf x Sb sample prepared in Example 1-7.
  • 2d is a graph showing the power factor ⁇ 2 ⁇ as a function of temperature for the FeNb 1-x Hf x Sb sample prepared in Example 1-7.
  • Figure 3 is a graph showing the zT value of the FeNb 1-x Hf x Sb sample prepared in Example 1-7 as a function of temperature.
  • Example 4 is a thermogravimetric analysis diagram of FeNb 0.86 Hf 0.14 Sb prepared in Example 1.
  • the raw materials were weighed according to the stoichiometric ratio of FeNb 0.86 Hf 0.14 Sb, placed in a copper tube protected by Ar gas, and repeatedly smelted three times by high frequency melting (positive high frequency electromagnetic field suspension smelting) to obtain ingots, and then mechanically.
  • the ball-milling method pulverizes the ingot to obtain submicron-sized small particles (particle diameter of about 200 nm to 2.0 ⁇ m), and then sintered at 850 ° C and 65 MPa for 10 minutes by a discharge plasma sintering method to obtain a final sample.
  • phase analysis of the sample prepared in this example was carried out by using a Rigaku D/MAX-2550PC type X-ray polycrystal diffractometer (XRD), as shown in Fig. 1, and confirmed as a FeNbSb-based structure, that is, a cubic structure (F43m), space.
  • the group number is 216.
  • the thermal conductivity ⁇ is calculated from the thermal diffusivity measured by the Netzsch LFA-457 laser pulse thermal analyzer, the specific heat measured by the Netzsch DSC-404 differential calorimeter, and the density of the material.
  • the samples were subjected to thermogravimetric analysis under nitrogen and air atmosphere using DSCQ1000 equipment. The test results are shown in Figure 4.
  • the heating rate is 15K/min and the temperature range is 300K-1200K. From 300K to 900K, the samples were kept stable under nitrogen, argon and air atmospheres, indicating that the prepared samples have good high temperature stability. Above 900K, the sample remained stable under nitrogen and argon atmospheres, but under air atmosphere, the weight increased slightly due to surface oxidation.
  • the raw materials were weighed according to the stoichiometric ratio of FeNb 0.88 Hf 0.12 Sb, placed in an Ar gas-protected copper tube, and repeatedly smelted three times by high-frequency melting to obtain an ingot, and then the ingot was obtained by mechanical ball milling to obtain a submicron.
  • the small particles (particle diameters of about 200 nm to 2.0 ⁇ m) were then sintered by a discharge plasma sintering method at 850 ° C and 65 MPa for 10 minutes to obtain a final sample.
  • the phase of the sample prepared in this example was analyzed by RigakuD/MAX-2550PC X-ray polycrystal diffractometer (XRD), as shown in Fig. 1, and confirmed as FeNbSb-based structure, ie cubic structure (F4 _ 3m)
  • the space group number is 216.
  • the raw materials were weighed according to the stoichiometric ratio of FeNb 0.8 Hf 0.2 Sb, placed in an Ar gas-protected copper tube, and repeatedly smelted three times by high-frequency melting to obtain an ingot, and then the ingot was obtained by mechanical ball milling to obtain a submicron.
  • the small particles (particle diameters of about 200 nm to 2.0 ⁇ m) were then sintered by a discharge plasma sintering method at 850 ° C and 65 MPa for 10 minutes to obtain a final sample.
  • the raw materials were weighed according to the stoichiometric ratio of FeNb 0.84 Hf 0.16 Sb, placed in an Ar gas-protected copper tube, and repeatedly smelted three times by high-frequency melting to obtain an ingot, and then the ingot was obtained by mechanical ball milling to obtain a submicron.
  • the small particles (particle diameters of about 200 nm to 2.0 ⁇ m) were then sintered by a discharge plasma sintering method at 850 ° C and 65 MPa for 10 minutes to obtain a final sample.
  • the raw materials were weighed according to the stoichiometric ratio of FeNb 0.9 Hf 0.1 Sb, placed in a copper tube protected by Ar gas, and repeatedly smelted three times by high-frequency melting to obtain an ingot, and then the ingot was obtained by mechanical ball milling to obtain submicron.
  • the small particles (particle diameters of about 200 nm to 2.0 ⁇ m) were then sintered by a discharge plasma sintering method at 850 ° C and 65 MPa for 10 minutes to obtain a final sample.
  • the raw materials were weighed according to the stoichiometric ratio of FeNb 0.92 Hf 0.08 Sb, placed in an Ar gas-protected copper tube, and repeatedly smelted three times by high-frequency melting to obtain an ingot, and then the ingot was obtained by mechanical ball milling to obtain a submicron.
  • the small particles (particle diameters of about 200 nm to 2.0 ⁇ m) were then sintered by a discharge plasma sintering method at 850 ° C and 65 MPa for 10 minutes to obtain a final sample.
  • the raw materials were weighed according to the stoichiometric ratio of FeNb 0.94 Hf 0.06 Sb, placed in an Ar gas-protected copper tube, and repeatedly smelted three times by high-frequency melting to obtain an ingot, and then the ingot was obtained by mechanical ball milling to obtain a submicron.
  • the small particles (particle diameters of about 200 nm to 2.0 ⁇ m) were then sintered by a discharge plasma sintering method at 850 ° C and 65 MPa for 10 minutes to obtain a final sample.
  • FIG. 3 is a graph showing the thermoelectric properties of the FeNb 1-x Hf x Sb samples. It can be seen from Fig. 2(a)-2(d) that the thermal conductivity and Seebeck coefficient of the sample continue to decrease with the increase of x, and the electrical conductivity increases with the increase of x.

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Abstract

A high figure of merit P-type FeNbHfSb thermoelectric material. The composition of the raw materials is FeNb1-xHfxSb, wherein x = 0.06-0.2. The P-type FeNbHfSb thermoelectric material is obtained as follows: firstly, weighing the raw materials of iron, niobium, hafnium and antimony according to a chemical dosage ratio of the composition FeNb1-xHfxSb, and melting the raw materials under the protection of argon to obtain an ingot; then crushing the ingot into particles, and then sintering the particles. The high temperature stability of the P-type FeNbHfSb thermoelectric material is good, the elements constituting the material are rich in the earth's crust, the preparation process is simple, the production cycle is short, the production efficiency is high, the industrialization cost is relatively low, and the maximum ZT value thereof reaches 1.45 at 1200 K.

Description

高优值的P型FeNbHfSb热电材料及其制备方法High-quality P-type FeNbHfSb thermoelectric material and preparation method thereof 技术领域Technical field
本发明涉及半导体热电材料领域，具体涉及一种高优值的P型FeNbHfSb热电材料及其制备方法。The invention relates to the field of semiconductor thermoelectric materials, in particular to a high-quality P-type FeNbHfSb thermoelectric material and a preparation method thereof.
背景技术Background technique
热电材料是一种通过材料内部的载流子(电子或空穴)运动实现电能和热能直接相互转换的半导体材料。当热电材料两端存在温差时，热电材料能将热能转化为电能输出，这个被称为Seebeck效应；而在热电材料两端加上电场后，热电材料能将电能转化为热能，一端放热而另一端吸热，被称为Petier效应，这两种效应分别使热电材料可以在发电或制冷等方面有广泛的应用背景。A thermoelectric material is a semiconductor material that directly converts electrical energy and thermal energy into each other through movement of carriers (electrons or holes) inside the material. When there is a temperature difference between the two ends of the thermoelectric material, the thermoelectric material can convert the thermal energy into the electric energy output, which is called the Seebeck effect; and after the electric field is applied to both ends of the thermoelectric material, the thermoelectric material can convert the electric energy into heat energy, and one end radiates heat. The other end of the heat absorption, known as the Petier effect, these two effects make thermoelectric materials have a wide range of applications in power generation or refrigeration.
用热电材料制造的发电装置可作为深层空间航天器、野外作业、海洋灯塔、游牧人群使用的电源，或用于工业余热、废热发电。用热电材料制造的制冷装置体积小、不需要化学介质，可应用于小型冷藏箱、计算机芯片和激光探测器等的局部冷却、医用便携式超低温冰箱等方面，更广泛的潜在应用领域将包括：家用冰箱、冷却，车用或家用空调装置等。用热电材料制造的装置具有无机械运动部件、无噪声、无磨损、结构简单、体积形状可按需要设计等突出优点。Power generation units made of thermoelectric materials can be used as power sources for deep spacecraft, field operations, marine lighthouses, nomadic people, or for industrial waste heat and waste heat power generation. The refrigerating device made of thermoelectric material is small in size and does not require chemical medium, and can be applied to local cooling of small refrigerators, computer chips and laser detectors, medical portable ultra-low temperature refrigerators, etc., and a wider range of potential application fields will include: household Refrigerator, cooling, car or home air conditioning units. The device made of thermoelectric material has the advantages of no mechanical moving parts, no noise, no wear, simple structure, and the shape can be designed as needed.
热电材料的性能用“热电优值”–zT进行表征：The performance of thermoelectric materials is characterized by the "thermoelectric merit" – zT:
zT＝(α2σT/κ)zT=(α 2 σT/κ)
α是材料的热电势系数，σ是电导率，T是绝对温度，κ是热导率。α is the thermoelectric potential coefficient of the material, σ is the electrical conductivity, T is the absolute temperature, and κ is the thermal conductivity.
一种好的热电材料应具有高的电导率和热电势系数和低的热导率，高性能的热电器件要求具有性能、结构相匹配的N型和P型材料。A good thermoelectric material should have high electrical conductivity and thermoelectric potential coefficient and low thermal conductivity. High-performance thermoelectric devices require N-type and P-type materials with matching performance and structure.
目前，高温发电热电材料在汽车工业、工厂废热回收、太空卫星等领域有着重要的应用。典型的高温发电热电材料为SiGe合金，其N型材料性能较高，zT值约为1.0，但P型材料性能较差，约为0.5。 At present, high-temperature power generation thermoelectric materials have important applications in the automotive industry, waste heat recovery in factories, and space satellites. A typical high-temperature power generation thermoelectric material is a SiGe alloy, and its N-type material has high performance, and the zT value is about 1.0, but the P-type material has poor performance, about 0.5.
近年来，Half-Heusler体系由于组成元素含量丰富，电学性能好等优点引起热电领域学者的关注。其中，N型ZrNiSn基Half-Heusler材料的zT值可达1.0，与N型SiGe相媲美。但是P型Half-Heusler材料的性能仍然较低，这是制约该体系在高温发电方面应用的一大难题。In recent years, the Half-Heusler system has attracted the attention of scholars in the field of thermoelectrics due to its rich content of components and good electrical properties. Among them, the N-type ZrNiSn-based Half-Heusler material has a zT value of 1.0, which is comparable to N-type SiGe. However, the performance of P-type Half-Heusler materials is still low, which is a major problem that restricts the application of this system in high-temperature power generation.
FeNbHfSb热电材料的原料在地壳中的储量丰富，价格相对低廉。但目前，对此类热电材料的研究却很少。The raw materials of FeNbHfSb thermoelectric materials are abundant in the earth's crust and the price is relatively low. However, at present, there are few studies on such thermoelectric materials.
发明内容Summary of the invention
本发明提供一种新型的高优值P型FeNbHfSb热电材料及其制备方法，所述P型FeNbHfSb热电材料的最高zT值在1200K时约为1.45。The invention provides a novel high-quality P-type FeNbHfSb thermoelectric material and a preparation method thereof, and the highest zT value of the P-type FeNbHfSb thermoelectric material is about 1.45 at 1200K.
本发明公开了一种高优值的P型FeNbHfSb热电材料，原料组成为FeNb1-xHfxSb，其中，x＝0.06～0.2，x代表原子百分比。The invention discloses a high-value P-type FeNbHfSb thermoelectric material, the raw material composition is FeNb 1-x Hf x Sb, wherein x=0.06-0.2, and x represents atomic percentage.
作为优选，x＝0.1～0.16，x在该范围取值时，zT均高于1.1；更进一步优选，x＝0.12～0.14，实验证明，x在该范围取值时，得到的FeNbHfSb热电材料在1200K时拥有最高的zT，zT在1.4以上，作为更以进一步优选，x＝0.12和x＝0.14，此时FeNbHfSb热电材料在1200K时的zT为1.45，可满足各种场合特殊使用。Preferably, x = 0.1 to 0.16, and when x is in the range, zT is higher than 1.1; more preferably, x = 0.12 to 0.14, and experiments have shown that when x is in the range, the obtained FeNbHfSb thermoelectric material is At 1200K, it has the highest zT, zT is above 1.4, and further preferred is x=0.12 and x=0.14. At this time, the zT of FeNbHfSb thermoelectric material at 1200K is 1.45, which can be used for various occasions.
本发明还公开了所述P型FeNbHfSb热电材料的制备方法，步骤如下：The invention also discloses a preparation method of the P-type FeNbHfSb thermoelectric material, the steps are as follows:
(1)按组成为FeNb1-xHfxSb的化学剂量比称取原料铁、铌、铪和锑，氩气保护下，经悬浮熔炼得到铸锭；(1) Weigh the raw materials of iron, bismuth, antimony and bismuth according to the chemical dosage ratio of FeNb 1-x Hf x Sb, and obtain the ingot by suspension smelting under the protection of argon gas;
(2)将步骤(1)得到的铸锭粉碎成颗粒，再经烧结得到所述的P型FeNbHfSb热电材料。(2) The ingot obtained in the step (1) is pulverized into pellets, and then sintered to obtain the P-type FeNbHfSb thermoelectric material.
作为优选，步骤(1)中，原料经悬浮熔炼法熔炼2-5次后得到铸锭。进一步优选为3次。Preferably, in the step (1), the raw material is smelted by suspension smelting for 2 to 5 times to obtain an ingot. More preferably, it is 3 times.
作为优选，步骤(2)中，铸锭粉碎成颗粒的粒度直径为200nm～10.0μm；进一步优选为200nm～2.0μm。这种粒度的颗粒有利于后续的烧结样品具有较低热导率，从而获得较高的热电性能。Preferably, in the step (2), the ingot is pulverized into particles having a particle diameter of 200 nm to 10.0 μm; more preferably 200 nm to 2.0 μm. Particles of this size help the subsequent sintered samples to have lower thermal conductivity, resulting in higher thermoelectric properties.
作为优选，步骤(2)中，经放电等离子烧结技术，烧结条件优选为：800-900℃，60-70MPa，烧结时间为10-15min；作为进一步优选，在850℃、65MPa下烧结10min，得到所述的P型FeNbHfSb热电材料。烧结温度过低或者压强过小会使得样品致密度过低，将会导致材料电导率下降，不利 于获得高性能的样品。烧结时间不宜过长，否则烧结试样的晶粒尺寸可能会继续长大，导致热导率升高，性能降低。Preferably, in the step (2), by the spark plasma sintering technique, the sintering conditions are preferably 800-900 ° C, 60-70 MPa, and the sintering time is 10-15 min; and further preferably, sintering at 850 ° C and 65 MPa for 10 min, The P-type FeNbHfSb thermoelectric material. If the sintering temperature is too low or the pressure is too small, the density of the sample will be too low, which will lead to a decrease in the conductivity of the material, which is unfavorable. For high performance samples. The sintering time should not be too long, otherwise the grain size of the sintered sample may continue to grow, resulting in an increase in thermal conductivity and a decrease in performance.
与现有技术相比，本发明具有的有益效果是：Compared with the prior art, the present invention has the following beneficial effects:
本发明制备了一种高优值P型FeNbHfSb热电材料，其最大zT值在1200K时达到1.45，这是目前P型Half-Heusler体系中获得的最高性能。The invention prepares a high-quality P-type FeNbHfSb thermoelectric material, and its maximum zT value reaches 1.45 at 1200K, which is the highest performance obtained in the current P-type Half-Heusler system.
本发明制备的P型FeNbHfSb热电材料，其材料成分所含的元素在地壳中的储量丰富，因此，生产成本相对低廉。The P-type FeNbHfSb thermoelectric material prepared by the invention has abundant reserves of elements contained in the material composition, and therefore, the production cost is relatively low.
本发明中P型FeNbHfSb热电材料的高温稳定性好、制备工艺简单、生产周期短，生产效率高。In the invention, the P-type FeNbHfSb thermoelectric material has high temperature stability, simple preparation process, short production cycle and high production efficiency.
附图说明DRAWINGS
图1为实施例1制备的FeNb0.86Hf0.14Sb和实施例2制备的FeNb0.88Hf0.12Sb的XRD图谱。1 is an XRD pattern of FeNb 0.86 Hf 0.14 Sb prepared in Example 1 and FeNb 0.88 Hf 0.12 Sb prepared in Example 2.
图2a为实施例1-7制备得到的FeNb1-xHfxSb试样的热导率κ随温度变化图。2a is a graph showing the change of thermal conductivity κ with temperature of the FeNb 1-x Hf x Sb sample prepared in Example 1-7.
图2b为实施例1-7制备得到的FeNb1-xHfxSb试样的电导率σ随温度变化图。2b is a graph showing the change in electrical conductivity σ of the FeNb 1-x Hf x Sb sample prepared in Example 1-7 as a function of temperature.
图2c为实施例1-7制备得到的FeNb1-xHfxSb试样的Seebeck系数α随温度变化图。2c is a graph showing the Seebeck coefficient α as a function of temperature for the FeNb 1-x Hf x Sb sample prepared in Example 1-7.
图2d为实施例1-7制备得到的FeNb1-xHfxSb试样的功率因子α2σ随温度变化图。2d is a graph showing the power factor α 2 σ as a function of temperature for the FeNb 1-x Hf x Sb sample prepared in Example 1-7.
图3为实施例1-7制备得到的FeNb1-xHfxSb试样的zT值随温度变化图。Figure 3 is a graph showing the zT value of the FeNb 1-x Hf x Sb sample prepared in Example 1-7 as a function of temperature.
图4为实施例1制备的FeNb0.86Hf0.14Sb的热重分析图。4 is a thermogravimetric analysis diagram of FeNb 0.86 Hf 0.14 Sb prepared in Example 1.
具体实施方式detailed description
以下结合实施例对本发明作进一步详细阐述。The invention will be further elaborated below in conjunction with the examples.
实施例1Example 1
将原料按化学剂量比FeNb0.86Hf0.14Sb计算称量后，置于Ar气保护的铜管中，采用高频熔炼(正高频电磁场悬浮熔炼)方法反复熔炼3次获得 铸锭，然后采用机械球磨方法粉碎铸锭获得亚微米级小颗粒(颗粒直径约为200nm～2.0μm)，接着采用放电等离子体烧结方法在850℃、65MPa条件下烧结10min，获得最终的试样。The raw materials were weighed according to the stoichiometric ratio of FeNb 0.86 Hf 0.14 Sb, placed in a copper tube protected by Ar gas, and repeatedly smelted three times by high frequency melting (positive high frequency electromagnetic field suspension smelting) to obtain ingots, and then mechanically. The ball-milling method pulverizes the ingot to obtain submicron-sized small particles (particle diameter of about 200 nm to 2.0 μm), and then sintered at 850 ° C and 65 MPa for 10 minutes by a discharge plasma sintering method to obtain a final sample.
采用RigakuD/MAX-2550PC型X射线多晶衍射仪(XRD)对本实施例制得的试样进行物相分析，如图1所示，并确认为FeNbSb基结构，即立方结构(F43m)，空间群号为216号。The phase analysis of the sample prepared in this example was carried out by using a Rigaku D/MAX-2550PC type X-ray polycrystal diffractometer (XRD), as shown in Fig. 1, and confirmed as a FeNbSb-based structure, that is, a cubic structure (F43m), space. The group number is 216.
根据采用Netzsch LFA-457型激光脉冲热分析仪测量的热扩散系数、采用Netzsch DSC-404型差分比热仪测量的比热以及材料的密度计算得到热导率κ。本实施例制得的试样的热导率在1200K时为κ＝4.25W·m-1K-1。The thermal conductivity κ is calculated from the thermal diffusivity measured by the Netzsch LFA-457 laser pulse thermal analyzer, the specific heat measured by the Netzsch DSC-404 differential calorimeter, and the density of the material. The thermal conductivity of the sample prepared in this example was κ = 4.25 W·m -1 K -1 at 1200 K.
采用Linses LSR-3设备测得材料在1200K时的热电势系数α＝230.8μV/K，电导率σ＝9.6×104S/m。The thermal potential coefficient α=230.8 μV/K of the material at 1200 K was measured by a Linses LSR-3 device, and the electrical conductivity σ=9.6×10 4 S/m.
根据上述测量值按zT＝(α2σT/κ)计算，本实施例制得的试样的zT值在1200K时约为1.45。According to the above measured value, zT = (α 2 σT / κ), the zT value of the sample prepared in this example was about 1.45 at 1200K.
采用DSCQ1000设备分别在氮气和空气氛围下对试样进行了热重分析，检测结果如图4所示，升温速率15K/min，温度范围300K-1200K。从300K到900K，试样在氮气，氩气和空气氛围下均保持重量稳定，这表明所制备的试样具有很好的高温稳定性。900K以上，试样在氮气和氩气氛围中仍然保持稳定，但是在空气氛围下，重量轻微增大，这是由于表面氧化引起的。The samples were subjected to thermogravimetric analysis under nitrogen and air atmosphere using DSCQ1000 equipment. The test results are shown in Figure 4. The heating rate is 15K/min and the temperature range is 300K-1200K. From 300K to 900K, the samples were kept stable under nitrogen, argon and air atmospheres, indicating that the prepared samples have good high temperature stability. Above 900K, the sample remained stable under nitrogen and argon atmospheres, but under air atmosphere, the weight increased slightly due to surface oxidation.
实施例2Example 2
将原料按化学剂量比FeNb0.88Hf0.12Sb计算称量后，置于Ar气保护的铜管中，采用高频熔炼方法反复熔炼3次获得铸锭，然后采用机械球磨方法粉碎铸锭获得亚微米级小颗粒(颗粒直径约为200nm～2.0μm)，接着采用放电等离子体烧结方法在850℃、65MPa条件下烧结10min，获得最终的试样。The raw materials were weighed according to the stoichiometric ratio of FeNb 0.88 Hf 0.12 Sb, placed in an Ar gas-protected copper tube, and repeatedly smelted three times by high-frequency melting to obtain an ingot, and then the ingot was obtained by mechanical ball milling to obtain a submicron. The small particles (particle diameters of about 200 nm to 2.0 μm) were then sintered by a discharge plasma sintering method at 850 ° C and 65 MPa for 10 minutes to obtain a final sample.
采用RigakuD/MAX-2550PC型X射线多晶衍射仪(XRD)对本实施例制得的试样进行物相分析，如图1所示，并确认为FeNbSb基结构，即立方结构(F4_3m)，空间群号为216号。 The phase of the sample prepared in this example was analyzed by RigakuD/MAX-2550PC X-ray polycrystal diffractometer (XRD), as shown in Fig. 1, and confirmed as FeNbSb-based structure, ie cubic structure (F4 _ 3m) The space group number is 216.
本实施例制得的试样的热导率在1200K时为κ＝4.19W·m-1K-1。The thermal conductivity of the sample prepared in this example was κ = 4.19 W·m -1 K -1 at 1200 K.
采用Linses LSR-3设备测得材料在1200K时的热电势系数α＝246μV/K，电导率σ＝8.4×104S/m。The thermal potential coefficient α=246μV/K of the material at 1200K was measured by Linses LSR-3 equipment, and the electrical conductivity σ=8.4×10 4 S/m.
根据上述测量值按zT＝(α2σT/κ)计算，本实施例制得的试样的zT值在1200K时约为1.46。According to the above measured value, zT = (α 2 σT / κ), the zT value of the sample prepared in this example was about 1.46 at 1200K.
实施例3Example 3
将原料按化学剂量比FeNb0.8Hf0.2Sb计算称量后，置于Ar气保护的铜管中，采用高频熔炼方法反复熔炼3次获得铸锭，然后采用机械球磨方法粉碎铸锭获得亚微米级小颗粒(颗粒直径约为200nm～2.0μm)，接着采用放电等离子体烧结方法在850℃、65MPa条件下烧结10min，获得最终的试样。The raw materials were weighed according to the stoichiometric ratio of FeNb 0.8 Hf 0.2 Sb, placed in an Ar gas-protected copper tube, and repeatedly smelted three times by high-frequency melting to obtain an ingot, and then the ingot was obtained by mechanical ball milling to obtain a submicron. The small particles (particle diameters of about 200 nm to 2.0 μm) were then sintered by a discharge plasma sintering method at 850 ° C and 65 MPa for 10 minutes to obtain a final sample.
本实施例制得的试样的热导率在1200K时为κ＝4.44W·m-1K-1。The thermal conductivity of the sample prepared in this example was κ = 4.44 W·m -1 K -1 at 1200 K.
采用Linses LSR-3设备测得材料在1200K时的热电势系数α＝199μV/K，电导率σ＝11×104S/m。The thermal potential coefficient α=199 μV/K of the material at 1200 K was measured by a Linses LSR-3 device, and the electrical conductivity σ=11×10 4 S/m.
根据上述测量值按zT＝(α2σT/κ)计算，本实施例制得的试样的zT值在1200K时约为1.18。Based on the above measured values, zT = (α 2 σT / κ), the zT value of the sample prepared in this example was about 1.18 at 1200K.
实施例4Example 4
将原料按化学剂量比FeNb0.84Hf0.16Sb计算称量后，置于Ar气保护的铜管中，采用高频熔炼方法反复熔炼3次获得铸锭，然后采用机械球磨方法粉碎铸锭获得亚微米级小颗粒(颗粒直径约为200nm～2.0μm)，接着采用放电等离子体烧结方法在850℃、65MPa条件下烧结10min，获得最终的试样。The raw materials were weighed according to the stoichiometric ratio of FeNb 0.84 Hf 0.16 Sb, placed in an Ar gas-protected copper tube, and repeatedly smelted three times by high-frequency melting to obtain an ingot, and then the ingot was obtained by mechanical ball milling to obtain a submicron. The small particles (particle diameters of about 200 nm to 2.0 μm) were then sintered by a discharge plasma sintering method at 850 ° C and 65 MPa for 10 minutes to obtain a final sample.
本实施例制得的试样的热导率在1200K时为κ＝5.1W·m-1K-1。The thermal conductivity of the sample prepared in this example was κ = 5.1 W·m -1 K -1 at 1200 K.
采用Linses LSR-3设备测得材料在1200K时的热电势系数α＝209μV/K，电导率σ＝10.8×104S/m。The thermal potential coefficient α=209μV/K of the material at 1200K was measured by Linses LSR-3 equipment, and the electrical conductivity σ=10.8×10 4 S/m.
根据上述测量值按zT＝(α2σT/κ)计算，本实施例制得的试样的zT值在1200K时约为1.2。 The zT value of the sample prepared in this example was about 1.2 at 1200 K, based on the above measured value, calculated as zT = (α 2 σT / κ).
实施例5Example 5
将原料按化学剂量比FeNb0.9Hf0.1Sb计算称量后，置于Ar气保护的铜管中，采用高频熔炼方法反复熔炼3次获得铸锭，然后采用机械球磨方法粉碎铸锭获得亚微米级小颗粒(颗粒直径约为200nm～2.0μm)，接着采用放电等离子体烧结方法在850℃、65MPa条件下烧结10min，获得最终的试样。The raw materials were weighed according to the stoichiometric ratio of FeNb 0.9 Hf 0.1 Sb, placed in a copper tube protected by Ar gas, and repeatedly smelted three times by high-frequency melting to obtain an ingot, and then the ingot was obtained by mechanical ball milling to obtain submicron. The small particles (particle diameters of about 200 nm to 2.0 μm) were then sintered by a discharge plasma sintering method at 850 ° C and 65 MPa for 10 minutes to obtain a final sample.
本实施例制得的试样的热导率在1200K时为κ＝4.22W·m-1K-1。The thermal conductivity of the sample prepared in this example was κ = 4.22 W·m -1 K -1 at 1200 K.
采用Linses LSR-3设备测得材料在1200K时的热电势系数α＝254μV/K，电导率σ＝7.2×104S/m。The thermal potential coefficient α=254 μV/K of the material at 1200 K was measured by a Linses LSR-3 device, and the electrical conductivity σ=7.2×10 4 S/m.
根据上述测量值按zT＝(α2σT/κ)计算，本实施例制得的试样的zT值在1200K时约为1.32。According to the above measured value, zT = (α 2 σT / κ), the zT value of the sample prepared in this example was about 1.32 at 1200K.
实施例6Example 6
将原料按化学剂量比FeNb0.92Hf0.08Sb计算称量后，置于Ar气保护的铜管中，采用高频熔炼方法反复熔炼3次获得铸锭，然后采用机械球磨方法粉碎铸锭获得亚微米级小颗粒(颗粒直径约为200nm～2.0μm)，接着采用放电等离子体烧结方法在850℃、65MPa条件下烧结10min，获得最终的试样。The raw materials were weighed according to the stoichiometric ratio of FeNb 0.92 Hf 0.08 Sb, placed in an Ar gas-protected copper tube, and repeatedly smelted three times by high-frequency melting to obtain an ingot, and then the ingot was obtained by mechanical ball milling to obtain a submicron. The small particles (particle diameters of about 200 nm to 2.0 μm) were then sintered by a discharge plasma sintering method at 850 ° C and 65 MPa for 10 minutes to obtain a final sample.
本实施例制得的试样的热导率在1200K时为κ＝4.67W·m-1K-1。The thermal conductivity of the sample prepared in this example was κ = 4.67 W·m -1 K -1 at 1200 K.
采用Linses LSR-3设备测得材料在1200K时的热电势系数α＝258μV/K，电导率σ＝5.92×104S/m。The thermal potential coefficient α=258μV/K of the material at 1200K was measured by Linses LSR-3 equipment, and the electrical conductivity σ=5.92×10 4 S/m.
根据上述测量值按zT＝(α2σT/κ)计算，本实施例制得的试样的zT值在1200K时约为1.01。According to the above measured value, zT = (α 2 σT / κ), the zT value of the sample prepared in this example was about 1.01 at 1200K.
实施例7Example 7
将原料按化学剂量比FeNb0.94Hf0.06Sb计算称量后，置于Ar气保护的铜管中，采用高频熔炼方法反复熔炼3次获得铸锭，然后采用机械球磨方法粉碎铸锭获得亚微米级小颗粒(颗粒直径约为200nm～2.0μm)，接着采用放电等离子体烧结方法在850℃、65MPa条件下烧结10min，获得最终 的试样。The raw materials were weighed according to the stoichiometric ratio of FeNb 0.94 Hf 0.06 Sb, placed in an Ar gas-protected copper tube, and repeatedly smelted three times by high-frequency melting to obtain an ingot, and then the ingot was obtained by mechanical ball milling to obtain a submicron. The small particles (particle diameters of about 200 nm to 2.0 μm) were then sintered by a discharge plasma sintering method at 850 ° C and 65 MPa for 10 minutes to obtain a final sample.
本实施例制得的试样的热导率在1200K时为κ＝5.58W·m-1K-1。The thermal conductivity of the sample prepared in this example was κ = 5.58 W·m -1 K -1 at 1200 K.
采用Linses LSR-3设备测得材料在1200K时的热电势系数α＝249.6μV/K，电导率σ＝4.47×104S/m。The thermal potential coefficient α=249.6μV/K of the material at 1200K was measured by Linses LSR-3 equipment, and the electrical conductivity σ=4.47×10 4 S/m.
根据上述测量值按zT＝(α2σT/κ)计算，本实施例制得的试样的zT值在1200K时约为0.6。The zT value of the sample prepared in this example was about 0.6 at 1200 K, based on the above measured value calculated as zT = (α 2 σT / κ).
热电性能分析：Thermoelectric performance analysis:
将实施例1-7制备得到的试样分别在不同温度进行热电性能检测，图3为FeNb1-xHfxSb试样的变温热电性能图。从图2(a)-2(d)中可以看到试样的热导率和Seebeck系数随x的增大持续降低，电导率则随x的增大而增大。按照zT＝(α2σT/κ)计算可得试样最终的zT值，发现所有样品的zT值均随温度上升而增大(图3所示)，作为最优选的试样x＝0.12和x＝0.14在1200K时拥有最高的zT＝1.45。分析发现，该试样拥有最高zT的原因在于其在1200K时有着最低的热导率(图2a)以及最高的功率因子(图2d)。 The samples prepared in Examples 1-7 were tested for thermoelectric properties at different temperatures, and FIG. 3 is a graph showing the thermoelectric properties of the FeNb 1-x Hf x Sb samples. It can be seen from Fig. 2(a)-2(d) that the thermal conductivity and Seebeck coefficient of the sample continue to decrease with the increase of x, and the electrical conductivity increases with the increase of x. The final zT value of the obtained sample was calculated according to zT=(α 2 σT/κ), and it was found that the zT values of all the samples increased with temperature (Fig. 3), as the most preferable sample x = 0.12 and x=0.14 has the highest zT=1.45 at 1200K. The analysis found that the sample had the highest zT because it had the lowest thermal conductivity at 1200 K (Fig. 2a) and the highest power factor (Fig. 2d).

Claims (9)

  1. 一种高优值的P型FeNbHfSb热电材料，其特征在于，原料组成为FeNb1-xHfxSb，其中，x＝0.06～0.2，x代表原子百分比。A high-value P-type FeNbHfSb thermoelectric material characterized in that the raw material composition is FeNb 1-x Hf x Sb, wherein x=0.06-0.2, and x represents an atomic percentage.
  2. 根据权利要求1所述的高优值的P型FeNbHfSb热电材料，其特征在于，x＝0.1～0.16。The high-value P-type FeNbHfSb thermoelectric material according to claim 1, wherein x = 0.1 to 0.16.
  3. 根据权利要求2所述的高优值的P型FeNbHfSb热电材料，其特征在于，x＝0.12～0.14。The high-value P-type FeNbHfSb thermoelectric material according to claim 2, wherein x=0.12 to 0.14.
  4. 根据权利要求3所述的高优值的P型FeNbHfSb热电材料，其特征在于，x＝0.12、x＝0.14。The high-value P-type FeNbHfSb thermoelectric material according to claim 3, wherein x = 0.12 and x = 0.14.
  5. 一种权利要求1～4任一权利要求所述的高优值的P型FeNbHfSb热电材料的制备方法，其特征在于，步骤如下：A method for preparing a high-value P-type FeNbHfSb thermoelectric material according to any one of claims 1 to 4, wherein the steps are as follows:
    (1)按组成为FeNb1-xHfxSb的化学剂量比称取原料铁、铌、铪和锑，氩气保护下，经悬浮熔炼法得到铸锭；(1) Weigh the raw materials of iron, bismuth, antimony and bismuth according to the chemical dosage ratio of FeNb 1-x Hf x Sb, and obtain the ingot by suspension smelting under the protection of argon gas;
    (2)将步骤(1)得到的铸锭粉碎成颗粒，再经烧结得到所述的P型FeNbHfSb热电材料。(2) The ingot obtained in the step (1) is pulverized into pellets, and then sintered to obtain the P-type FeNbHfSb thermoelectric material.
  6. 根据权利要求5所述的高优值的P型FeNbHfSb热电材料的制备方法，其特征在于，步骤(1)中，原料经悬浮熔炼法熔炼2-5次后得到铸锭。The method for preparing a high-value P-type FeNbHfSb thermoelectric material according to claim 5, wherein in the step (1), the raw material is smelted by suspension smelting for 2 to 5 times to obtain an ingot.
  7. 根据权利要求5所述的高优值的P型FeNbHfSb热电材料的制备方法，其特征在于，步骤(2)中，铸锭粉碎成颗粒的粒度直径为200nm～10.0μm。The method for producing a high-value P-type FeNbHfSb thermoelectric material according to claim 5, wherein in the step (2), the ingot is pulverized into particles having a particle diameter of 200 nm to 10.0 μm.
  8. 根据权利要求5-7任一权利要求所述的高优值的P型FeNbHfSb热电材料的制备方法，其特征在于，步骤(2)中，采用放电等离子烧结工艺进行烧结，烧结条件为：烧结温度为800-900℃，烧结压强为60-70MPa，烧结时间为10-15min。The method for preparing a high-value P-type FeNbHfSb thermoelectric material according to any one of claims 5-7, wherein in the step (2), sintering is performed by a spark plasma sintering process, and the sintering condition is: sintering temperature It is 800-900 ° C, the sintering pressure is 60-70 MPa, and the sintering time is 10-15 min.
  9. 根据权利要求8所述的高优值的P型FeNbHfSb热电材料的制备方法，其特征在于，步骤(2)中，烧结条件为：烧结温度为850℃，烧结压强为65MPa，烧结时间为10min。 The method for preparing a high-value P-type FeNbHfSb thermoelectric material according to claim 8, wherein in the step (2), the sintering conditions are: a sintering temperature of 850 ° C, a sintering pressure of 65 MPa, and a sintering time of 10 min.
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